CN1918126B - Ionic UV-A sunscreens and compositions containing them - Google Patents

Abstract

The present invention relates to novel 1,4-dihydropyridine derivatives, to novel cosmetic or dermatological sunscreen compositions containing these derivatives and the use of these derivatives for photoprotecting human skin and/or hair against UV radiation, in particular solar radiation.

Description

Ionic UV-A sun-screening agent and contain the composition of this sun-screening agent

The present invention relates to new 1; new sun-screening agent (sunscreen) composition that 4-dihydrogen pyridine derivative, the cosmetic that contains this derivative or dermatology are used; and this analog derivative is to people's skin and/or hair ultraviolet radiation resisting, and especially the application of photoirradiation protection is carried out in the anti-sun light irradiation.

In accepting the crowd that harmful amount of sunlight increases, the requirement of preventing coating protection agent is continued to increase.Sun exposure can cause that skin changes repeatedly, i.e. photoaging skin.The visible clinical change is different from the clinical change of the normal aging skin at the anti-solar exposure position of human body in photoaging skin.In the damage result of skin big area Exposure to Sunlight, corrugate, before the elastosis, pigment variation, canceration and the carninomatosis skin injury more and more.

Past, developed many sun-screening agent chemical, can to UV-A (320～400nm) and/or UV-B (290～320nm) wavelength and even more short wavelength's (UV-C) deleterious effect protect.These chemical or separately or mutually combination join be widely known by the people and widely used cosmetic or pharmaceutical preparation in.

Particularly UV-A irradiation can cause quick, direct faint cutaneous pigmentation.UV-A ray transdermal deep layer, and can quicken ageing processes of skin there.Irradiation than shortwave UV-A II promotes sunburn to form.The irradiation of UV-A II can also and then cause phototonus (phototonic) or photo sensitive reaction.Between UV-A irradiation and the increasing skin carcinoma danger relation is arranged.

Although a large amount of safe and effective UV-B absorption agents are arranged, be suitable for protecting people's the UV-A absorption agent of skin rather limited for number.Well behaved UV-A absorption agent should have good light stability, toxicology and dermatology acceptability, remarkable thermostability, the splendid solubility in the makeup solvent, the solubility in oil or water particularly, with stability in 4～9 scopes of the consistency of base material of cosmetics, pH value, add processability in the make-up preparation, with the consistency of other make-up preparation compositions and wrapping material, do not stain textiles, the flavor of smelling of should be colourless, having natural or smelling good, and should not have viscosity, and has low volatility.Especially to the goods that are used for hair such as hairspray, shampoo, hair care product etc., must meet strict requirement, and the UV absorption agent must stick on the hair, so that sufficient protection to be provided.

Oil soluble sun-screening agent in UV-A scope tool sorption for instance, is disclosed among the WO03/068183.

Satisfying the available UV-A absorption agent kind number of at least some requirements in the above-mentioned various requirement, this is just few, and is water-soluble or be applicable to that the UV-A absorption agent kind number of hair is even still less.The advantage of water-soluble UV-A sun-screening agent is to be introduced into the aqueous phase of oil-in-water-type or water-in-oil emulsion.Because in these emulsions, water is more than oil phase usually, the sun-screening agent that therefore can add water is more than the sun-screening agent that can add oil phase, thereby obtains the composition of higher SPF (sun protection factor).And, water-soluble UV-A opalizer can with the known oil-soluble UV-A opalizer combination in the oil phase of two phase emulsion, this also can cause SPF (sun protection factor) to increase.

For instance, disclose some water-soluble UV-A sun-screening agents among the EP-A 669 323, both disclosed water-soluble sun-screening agent in this patent application, also disclose the oil soluble sun-screening agent.Yet disclosed water-soluble UV-A sun-screening agent in this document, compound phenyl bisbenzimidazole tetrasulfonic acid disodium for example, its absorption peak be at the 335nm place, and extinction value E only is 745, and this value is lower.It is preferred that absorption peak is situated between between 350～370nm.In addition, also preferably use water-soluble and/or advantageously stick on the hair, that extinction value E is high, as to improve sun-screening agent effect UV-A sun-screening agent.The E value is preferably greater than 1000 greater than 900, and for example 1000～1200th, very favorable.

Also disclose some UV-A sun-screening agents among the DE 33 24 735, and more disclosed sun-screening agents also are water miscible in this document.The example of this water-soluble UV-A sun-screening agent is Terephthalidene Dicamphor Sulfonic Acid (terephthalylidene dicamphor sulfonic acid), yet the optical extinction coefficient E of this compound only is 866, and absorption peak is at the 345nm place.

The current needs that still exist more UV-A sun-screening agents, this sun-screening agent be water miscible and/or can stick on the hair, not only meet top pointed sun-screening agent requirement, and but on quite high wavelength, also have absorption peak, preferably between 350～370nm, and has a fabulous E value, preferred 900 or higher, more preferably 1000 or higher.

Compound shown in the general formula I has been realized this purpose

In the formula,

R ¹And R ²Be identical or different suction electric charge subbase group, perhaps R ¹And R ²In one be hydrogen, and another person is for inhaling electric charge subbase group,

R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen atom, C ₁-C ₁₀Alkyl, C ₂-C ₁₀Alkenyl, C ₂-C ₁₀Alkynyl, C ₃-C ₁₀Cycloalkyl or, C ₆-C ₁₀Aryl, above-mentioned each group is replaced by 1 to 3 substituting group by unsubstituted or optional, and described substituting group is selected from C ₁-C ₆Alkyl, halogen, hydroxyl and C ₁-C ₆Alkoxyl group, perhaps R ³And R ⁵And/or R ⁴And R ⁶Constitute 5 yuan or 6 yuan of rings together with the carbon atom that it connected, these 5 yuan or 6 yuan ring is optional to be replaced by 1 to 4 substituting group, and described substituting group is selected from C ₁-C ₆Alkyl, C ₃-C ₆Cycloalkyl, C ₁-C ₆Alkoxyl group, hydroxyl or halogen,

X is for containing 1 to 20 carbon atom and optional 1 to 10 heteroatoms, and contains the alkyl of the group of at least one lotus positive electricity or bear electricity, and

Y is counter ion.

As used in the present specification, term " electron-withdrawing group " is meant that those contain the group of multikey, for example is preferably cyano group or nitrilo (CN group), perhaps-and COOR ⁸,-COR ⁸Or-CONR ⁸ ₂Group, each R in the formula ⁸Be hydrogen, C independently of one another ₁-C ₂₁Alkyl (preferred C ₁-C ₆Alkyl), C ₂-C ₂₁Alkenyl (preferred C ₂-C ₆Alkenyl), C ₂-C ₂₁Alkynyl (preferred C ₂-C ₆Alkynyl), C ₃-C ₂₁Cycloalkyl (preferred C ₃-C ₈Cycloalkyl) or C ₆-C ₁₀Aryl (preferred phenyl), each group in these groups or the preferred group are not substituted or are optional by 1～3 substituting group replacement, and substituting group is selected from C ₁-C ₆Alkyl, halogen, hydroxyl and C ₁-C ₆Alkoxyl group.Preferably, radicals R ¹And R ²In at least one be cyano group, most preferably, radicals R ¹And R ²Be cyano group (CN group).Also preferably, a group is a cyano group, and another group is-COOR ⁸

R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen atom, C ₁-C ₁₀Alkyl, C ₂-C ₁₀Alkenyl, C ₂-C ₁₀Alkynyl, C ₃-C ₁₀Cycloalkyl and C ₆-C ₁₀Aryl.Each group in these groups can be unsubstituted, is perhaps replaced by 1 to 3 substituting group, and described substituting group is selected from C ₁-C ₆Alkyl, halogen, hydroxyl and C ₁-C ₆Alkoxyl group.As another kind of selection scheme, also can make R ³And R ⁵And/or R ⁴And R ⁶Constitute 5 yuan or 6 yuan of rings together with the carbon atom that it connected, these 5 yuan or 6 yuan ring is optional to be replaced by 1 to 4 substituting group, and described substituting group is selected from C ₁-C ₆Alkyl, C ₃-C ₆Cycloalkyl, C ₁-C ₆Alkoxyl group, hydroxyl or halogen.Preferably, R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen atom, C ₁-C ₆Alkyl, C ₂-C ₆Alkenyl, C ₅-C ₈Cycloalkyl and phenyl, each group in these groups is optional to be replaced by 1～3 substituting group, more preferably, is replaced by a substituting group as defined above.Also preferably, R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen atom and unsubstituted C ₁-C ₆Alkyl, C ₂-C ₆Alkenyl, C ₅-C ₈Cycloalkyl and phenyl.If R ³And R ⁵And/or R ⁴And R ⁶Constitute 5 yuan or 6 yuan of rings together with the carbon atom that it connected, then be preferably 6 yuan of rings, and should preferably not replace or be replaced by ring by a substituting group as defined above.

Most preferably, R ³, R ⁴, R ⁵And R ⁶In at least one, more preferably R ³, R ⁴, R ⁵And R ⁶In two be hydrogen atom, and R ³, R ⁴, R ⁵And R ⁶Other groups in the group are C ₁-C ₆Alkyl or C ₂-C ₆Alkenyl.R most preferably ³And R ⁴Be hydrogen atom, and R ⁵And R ⁶Be C ₁-C ₆Alkyl or C ₂-C ₆Alkenyl, more preferably C ₁-C ₃Alkyl.

Alkyl can be side chain or straight chain.C ₁-C ₁₀The preferred example of alkyl is methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, isobutyl-, amyl group, neo-pentyl, hexyl, 2-ethylhexyl and octyl group.

C ₃-C ₁₀The preferred example of cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.

C ₂-C ₆The preferred example of alkenyl is vinyl and positive propenyl.

C ₆-C ₁₀The preferred example of aryl is phenyl and naphthyl.

X is for containing 1 to 20 carbon atom, preferred 1 to 10 carbon atom, more preferably 1 to 6 carbon atom and optional 1 to 10 heteroatoms, preferred 1 to 6 heteroatomic straight chain, side chain, ring-type or aromatic hydrocarbyl of containing.According to this specification sheets, contain heteroatomic alkyl and also can contain functional group such as hydroxyl.Heteroatoms is preferably selected from O, N, S and P atom.For the present invention, importantly, radicals X comprises at least one group, preferably includes the group of 1,2 or 3 lotus positive electricity or bear electricity.X is preferably alkyl, aryl, alkaryl, the alkyl-cycloalkyl that contains 1 to 20 carbon atom and optional 1 to 10 heteroatoms and comprise at least one lotus positive electricity or bear electric group.Term " alkaryl " or " alkyl-cycloalkyl " mean aryl or the cycloalkyl that contains one or more alkyl substituents.Because radicals X comprises the group of at least one lotus positive electricity or bear electricity, so it contains the heteroatoms of at least one lotus positive electricity or bear electricity usually.Preferably, the X group contains 1 to 6 heteroatoms, and described heteroatoms is preferably selected from nitrogen, oxygen, sulphur or phosphorus atom.If radicals X lotus positive electricity, the then preferred nitrogen-atoms that contains a lotus positive electricity at least, thereby the group of this lotus positive electricity is a quaternary ammonium group.This compound of quaternary ammonium ion that comprises is particularly preferred for hair.If radicals X contains the bear electric group, then this bear electric group is preferably acidic group, for example phosphate or sulfate or carboxylic acid residues.

The X group also can contain 1 to 4 unsaturated C-C, preferred two keys.Each carbon atom can be chosen wantonly by functional group and replace in the X group, specifically, by hydroxyl or amino the replacement, is preferably replaced by hydroxyl.Define in the X group of replacement no more than 3 of substituted carbonatoms above preferred, more preferably no more than 2.Certainly, if the carbon atom in the X group is replaced by amino, may be unsaturated link(age) also between carbon atom and the nitrogen-atoms then, be preferably two keys.Also possible is that X group and Y group constitute the zwitter-ion structure jointly.

If the group bear electricity of lotus positive electricity or bear electricity in the X group, negative charge of the preferred lotus of X group then, and most preferably be acidic group for example-O-SO ₃ ^-,-COO ^-,-O-PO ₃H ^-,-O-PO ₃ ^2-,-SO ₃ ^-,-PO ₃H ^-Or-PO ₃ ^2-Most preferably be-O-SO ₃ ^-,-SO ₃ ^-With-O-PO ₃H ^-The X group that comprises at least one bear electric group, its exemplary is for choosing wantonly by the alkylidene group of cycloalkyl or aryl replacement, by cycloalkyl or aryl alkylidene group at interval and the alkylidene group that contains the top acidic group that defines.In a kind of preferred embodiment, this alkylidene group is by 1 to 3 heteroatoms interval, and described heteroatoms is preferably selected from oxygen and nitrogen-atoms interval, and described heteroatoms is preferably selected from oxygen, nitrogen-atoms and nitrogen-atoms.This alkylidene group preferably contains 1 to 10 carbon atom, more preferably contains 1 to 6 carbon atom.If this alkylidene group by nitrogen-atoms at interval, then this nitrogen-atoms also has radicals R as defined above ⁸

The preferred embodiment of the X group of the single negative charge of lotus is a group

-(C (R ⁹ ₂)) _n-(V) _m-(C (R ⁹ ₂)) _o-(U) _p-(C (R ⁹ ₂)) _q-W, each R in the formula ⁹Be hydroxyl independently, R perhaps as defined above ⁸Group also is preferably hydrogen atom, hydroxyl or C ₁-C ₃Alkyl, V and U are heteroatoms independently, and (this nitrogen-atoms also has R as defined above to be preferably Sauerstoffatom or nitrogen-atoms ⁸Group), Sauerstoffatom more preferably, n is 0～6 integer (being preferably 1～6), m is 0 or 1, o is 0～6 integer (being preferably 1～6), and p is 0 or 1, and q is 0～6 integer (being preferably 1～6), and W is the group of bear electricity, is preferably acidic group as defined above, most preferably is-O-PO ₃H ^-,-SO ₃ ^-Perhaps-O-SO ₃ ^-, precondition is, the total number of carbon atoms is 20 or still less, be preferably 10 or still less, most preferably be 1～6, precondition is that the heteroatoms sum comprises that the heteroatoms among the W of functional group is 1～10 in the X group simultaneously, its precondition is, if subscript m and p are 1, then subscript o is not 0.Preferred no more than 4 R ⁹Group, more preferably no more than 2 R ⁹Group is different from hydrogen, most preferably all R ⁹Group is hydrogen.

Another preferred embodiment of the X group of the single negative charge of lotus is a group

-Ar-W，

In the formula, Ar is an aromatic group, preferred C ₆-C ₁₀Aryl such as phenylene or naphthylidene, perhaps heterocyclic group is preferably 4～10 yuan of rings, wherein one or more, preferred 1 or 2 annular atoms is a heteroatoms, is preferably N, O or S.This heterocyclic group can be saturated or undersaturated group, and heteroaromatic group, and for example pyridylidene also is included in wherein.W is person as defined above.

Further preferably, at least one group of lotus positive electricity or negative electricity is the group of a positive charge of lotus in the X group.Most preferably this group of a positive charge of lotus is a quaternary ammonium group.In the case, the X group is preferably the group shown in the following formula

In the formula, each R ¹⁰Be hydrogen or R independently ¹¹, and each R ¹¹Independently with top defined R ⁸, be preferably hydrogen, C ₁-C ₁₀Alkyl, being preferably can be by 1 to 4 heteroatoms C at interval ₁-C ₆Alkyl is preferably by 1 or 2 heteroatoms C at interval ₁-C ₆Alkyl is preferably by 1 or 2 Sauerstoffatom C at interval ₁-C ₆Alkyl, and this C ₁-C ₁₀Alkyl can be selected from hydroxyl, amino and C by 1 to 3 ₁-C ₆Alkyl (preferred C ₁-C ₃Alkyl) substituting group replaces, subscript r is 1～10 integer, be preferably 1～6 integer, precondition is, the total number of carbon atoms is 20 or less than 20 in the X group, and is preferred 1～10, and comprises that the heteroatoms sum of all heteroatomss in nitrogen-atoms and the functional group is preferably 1～10, preferred 1～6, more preferably 1～4.Comprise at least one as defined above the compound of quaternary ammonium ion be specially adapted to hair, for example hair care product, shampoo, hair jelly or the like.In one embodiment of the invention, R ¹¹Group can contain a negative charge, thereby comprises Y group, for example a R ¹¹Group can be by bear electricity functional group as-SO ₃ ^-Or the alkyl of similar group replacement.

In a preferred embodiment, the XY group is the zwitter-ion of hold concurrently lotus positive electricity and negative electricity, and its carbonatoms, heteroatoms number and functional group's number are as defined above.

The definite structure of X group and irrelevant is as long as its lotus has at least one can make molecule water-soluble and/or positive charge or negative charge with the cohesive force of hair be provided.Preferably, X contains one, two or three positive charges or negative charge.

Y group be should balance X group electric charge counter ion.The definite chemical property of counter ion Y is not critical to the present invention, as long as counter ion Y does not play detrimentally affect to the advantageous characteristic of UV-A absorption agent, and especially as long as Y can give acceptance on dermatology and aspect the makeup.If X group bear, then Y group is preferably quaternary ammonium ion, alkalimetal ion or alkaline-earth metal ions, more preferably sodium ion, potassium ion, calcium ion or magnesium ion, but Y group also can be the organic group of lotus positive electricity, for instance, ammonium ion such as triethanol ammonium ion, amino methyl propyl alcohol ion or trometamol (tromethamine) ion.If Y group institute lotus positive electricity is more than X group institute bear electricity, then Y group also contains the counter ion of the unnecessary electric charge of energy balance, perhaps comes above X group of balance with a Y group.For instance, Y group can be Or M ^S+(A-) _S-1, M wherein ^S+Be lotus carbonium, A ^-Be the ion such as the halogen atom of the single negative charge of lotus, s is 1～3, preferred 1 or 2, more preferably 1.

If X group lotus positive electricity, then Y bear electricity, and Y group are preferably halogen atom such as chlorine atom, bromine atoms or iodine atom.If Y group institute bear electricity is more than X group institute lotus positive electricity, then Y group also contains the counter ion of the unnecessary electric charge of energy balance, perhaps comes above X group of balance with a Y group.For instance, Y group can be (M ^S-) or M ^S-(A ⁺) _S-1, M wherein ^S-Be bear electron ion, A ⁺Be the ion such as the alkalimetal ion of the single positive charge of lotus, s is 1～3, preferred 1 or 2, more preferably 1.

If then can there be above Y counter ion in above electric charge of X group band, the perhaps Y group band electric charge that contends with more than.Importantly, select Y group to make the neutral on the whole of molecule shown in the formula I.

X and Y are combined, just as at-(CH with chemical mode ₂) _rN ⁺(R ¹¹) ₂-(CH ₂) _t-SO ₃ ^-Like that, wherein r is the same defines in the part, and t is 1～10 integer, is preferably 1～5 integer, and for example 2.In each embodiment of this situation, X group and Y group constitute the zwitter-ion structure jointly.

The preferred R that selects ¹To R ⁶, X and Y make the solubleness of molecule be at least 10g/l, preferably is at least 50g/l, more preferably is at least 100g/l.If the solubleness of compound shown in the formula I is enough not big, then can change substitute mode, for example can reduce R ³To R ⁶Carbonatoms in the group can be removed aryl or the group of naphthene base that solubleness is reduced from some or all groups, and can contain the hydrophilic substituent such as hydroxyl.

To the compound of the very big cohesive force of hair tool as top definition general formula-C (R ¹⁰ ₂) _r-N ⁺(R ¹¹) ₃Quaternary ammonium ion, its solubleness may be lower.

The preferred compound of the present invention is

And the combination or the exchange of different structure unit (structure element).

Compound

With

Water-soluble may be little, but they are particularly preferred for hair nursing.

Compound shown in the formula I can prepare with known method itself.Have certain methods to be disclosed among the embodiment, these those skilled in the art can adopt these methods to come other compounds shown in the preparation formula I easily.

Wherein X ' is the front body structure of XY.

-O-PO ₃ ^2-The phosphate radical residue of type can be for example by corresponding alcohol functional group as using POCl ₃With alkali triethylamine (for example referring to M.-Z.Liu et al., Carbohy dr.Res.330 (3), 413-420 (2001)) for example, with P ₂O ₅And H ₃PO ₄(for example referring to K.Buss et al., J.Med.Chem.44 (19), 3166-3174 (2001)) or prepare by enzymatic means.

-O-SO ₃ ^-The sulfate radical residue of type can be for example by corresponding alcohol functional group as using SO ₃* pyridine (for example referring to W.J.Sanders et al., Tetrahedron 53 (48), 16391-16422 (1997)) and SO ₃* NEt ₃(for example referring to B.Ferla et al., Tetrahedron 55 (32), 9867-9880 (1999)), chlorsulfonic acid (for example referring to G.Dekany et al., J.Carbohy dr.Chem.16 (1), 11-24 (1997)) or H ₂SO ₄(for example referring to S.P.Gaur et al., Indian J.Chem.Sect.B21 (1), 46-51 (1982)) preparation.

Preferred compounds more of the present invention and general preparation method thereof are as follows:

Method a)

Method b)

Be similar to:

Method c)

Be similar to:

Method d)

Be similar to:

Method e)

The same

Method f)

Method g)

Method h)

Method i)

Method j)

Be similar to embodiment 2:

Be similar to embodiment 1:

Compound is especially preferred shown in the following general formula (I):

R ¹And R ²Group is cyano group, radicals R ³, R ⁴, R ⁵And R ⁶Be selected from hydrogen atom and C independently of one another ₁-C ₆Alkyl, Y are the counter ion of balance X group electric charge, decide according to the electric charge of X, are preferably alkalimetal ion or halogen ion, and

A) X is a group

-(C(R ⁹ ₂)) _n-(V) _m-(C(R ⁹ ₂)) _o-(U) _p-(C(R ⁹ ₂)) _q-W，

Each R in the formula ⁹Be hydrogen, hydroxyl or C independently of one another ₁-C ₃Alkyl, V and U are Sauerstoffatom, and n is 1～3 integer, and m is 0 or 1, and p is 0 or 1, and wherein at least one is 1 among m and the p, and o is 1～3 integer, and q is 1～3 integer, and W is-O-PO ₃H ^-Group or-O-SO ₃ ^-Group, perhaps

B) X is a group

In the formula, each R ¹⁰Group is independently selected from hydrogen atom, hydroxyl and C ₁-C ₃Alkyl, and R ¹¹Group is independently selected from hydrogen atom and optional by 1 to 2 Sauerstoffatom interval and the optional C that is replaced by 1 to 3 hydroxyl ₁-C ₆Alkyl, and r is 1～6 integer, perhaps

C) X is a group

-(C(R ⁹ ₂)) _n-(V) _m-(C(R ⁹ ₂)) _o-(U) _p-(C(R ⁹ ₂)) _q-W，

R in the formula ⁹Be respectively hydrogen or methyl separately, V and U are Sauerstoffatom, and n is 1～3 integer, and m is 0 or 1, and p is 0 or 1, and wherein at least one is 1 among m and the p, and o is 1～3 integer, and q is 1～3 integer, and W is-O-PO ₃The H-group or-O-SO ₃ ^-Group, perhaps

B) X is a group

In the formula, R ¹⁰Group is selected from hydrogen atom, hydroxyl and C respectively ₁-C ₃Alkyl, and R ¹¹Group is selected from hydrogen atom and optional by 1 to 2 Sauerstoffatom interval and the optional C that is replaced by 1 to 3 hydroxyl respectively ₁-C ₆Alkyl, and r is 1～3 integer, perhaps

E) X is a group

-(C(R ⁹ ₂)) _n-(V) _m-(C(R ⁹ ₂)) _o-W，

In the formula, R ⁹Be hydrogen or methyl independently of one another, V is a Sauerstoffatom, and n is 1～3 integer, and m is 1, and o is 1～3 integer, and W is group-O-PO ₃H ^-Or-O-SO ₃ ^-, perhaps

F) X is a group shown in the following formula

In the formula, radicals R ¹⁰Be selected from hydrogen atom and C independently of one another ₁-C ₃Alkyl, radicals R ¹¹Be selected from optional independently of one another by 1 or 2 heteroatoms interval and the optional C that is replaced by 1 to 3 hydroxyl ₁-C ₆Alkyl, and r is 1～3 integer, perhaps

G) X is a group shown in the following formula

-(C(R ⁹ ₂)) _n-W，

In the formula, each R ⁹Be hydrogen, hydroxyl or C independently of one another ₁-C ₃Alkyl, n are 1～6 integer, and W is group-O-PO ₃H ^-Or-O-SO ₃ ^-, perhaps

H) X is a group shown in the following formula

In the formula, R ¹⁰Be selected from hydrogen atom, hydroxyl and C independently of one another ₁-C ₃Alkyl, two R ¹¹Group is C ₁-C ₃Alkyl, a R ¹¹Group is interrupted by 1 or 2 Sauerstoffatom and the optional C that is replaced by 1 to 3 hydroxyl for optional ₁-C ₆Alkyl, and r is 1～3 integer, perhaps R ¹¹Group and nitrogen-atoms constitute pyridyl jointly, and this pyridyl is not substituted, perhaps by 1 to 5, preferably by the substituent R that defines above 1 to 3 ⁸Replace.

I) above a) to h) in the group in each group of defining, one of them radicals R ⁹Or R ¹⁰For saturated or undersaturated, contain the nitrogenous alkyl of 5 carbon atoms and one or two nitrogen-atoms at the most.

The solubleness of The compounds of this invention that contains following groups is high especially, and compound is particularly preferred shown in the general formula (I):

Shown in group be not substituted, perhaps by 1 to 5, preferred 1 to 3 substituent R as defined above ⁸Replace.

The invention still further relates to the various compound compositions shown in the general formula (I) that is formulated in appropriate carrier or the base-material that contain.Representative is, the present composition is used for protecting the material to the ultraviolet irradiation sensitivity, and especially to the material of solar radiation sensitivity, described composition comprises compound shown at least a general formula (I) of effective illumination protective number.In a preferred embodiment of the invention, this composition is suitable for protecting skin and/or hair not to be subjected to the deleterious effect of ultraviolet irradiation.In the case, composition of the present invention is make-up composition or pharmaceutical composition, and it comprises that acceptable vehicle of local available, makeup or pharmacology or thinner make carrier.According to another embodiment of the invention, compound can add in the plasticity base-material shown in the general formula (I).Compound shown in the general formula (I) also can be used to make local stable with the photosensitive composition in the preparation, especially tinting material, for example FD﹠amp; C, D﹠amp; The C tinting material, turmeric yellow (curcumin), riboflavin (riboflavine), riboflavin (lactoflavine), Tartrazol yellow (tartrazine), quinoline Huang (chinolinyellow), cochineal (cochenille), azorubin (azorubine), amaranth, ponceau 4R, erythrosine (erythrosin), indigo-blue, chlorophyll (chlorophylle), CHLOROPHYLLINE, caramel, Medicinal Charcoal, carotenoid, bixin, norbixin (norbixin), aronotta (annatto), capsanthin (orlean), Capsanthin (capsanthin), Capsorubin (capsorubin), lycopin (lycopin), xenthophylls (xanthophylle), flavoxanthin (flavoxanthin), xenthophylls (lutein), cryptoxanthin (kryptoaxanthin), rubixanthin (rubixanthin), zeaxanthin diepoxide (violaxanthin), rhodoxanthin (rhodoxanthin), canthaxanthin (canthaxanthin), betanin (betanin), anthocyan (anthocyan), VITAMIN such as vitamin A, vitamin K1, vitamins C, perhaps other activeconstituentss.

The obtained the maximum absorption of compound is in the UV-A zone shown in the general formula (I).For the purpose of the preparation sun-screening agent; especially use and/or Toiletry preparation for the preparation dermatology; for the purpose of the skin care or sunscreen formulas goods in for example daily makeup, compound shown in the general formula (I) can be spiked in the auxiliary agent, for example be spiked into the base material of cosmetics that is used for these prescription goods routinely.Under occasion easily, also can add other UV-A or UV-B sun-screening agents commonly used, be preferably pigment.Uv filters meeting show synergistic is adopted in combination.The preparation of above-mentioned sun-screening agent, this field those of skill in the art all know.The concentration of uv filters can change in the scope of broadness.For instance, the amount of the optional extra wetting ability outside the compound and/or lipotropy UV-A or UV-B sun-screening agent shown in compound shown in the general formula (I) and the general formula (I) can be in 0.5～12% (weight) scope that is as the criterion in composition total weight.These extra sun-screening agents are favourable to be selected from following compounds, but are not limited to these compounds:

UV-B or wide spectrum sun-screening agent, also be obtained the maximum absorption at about material of 290 to 340nm, its example that is used in combination with The compounds of this invention that is considered for example is following organic compound and mineral compound:

---acrylate, for example Viosorb 930 (octocrylene, PARSOL

340), 2-cyano-3,3-diphenyl ethyl acrylate etc.;

---camphor derivatives, for example 4 methyl benzylidene camphor (PARSOL

5000), 3-benzylidene camphor, camphor benzalkonium methylsulfuric acid ester, polyacrylamide base methyl benzylidene camphor, sulfo group benzylidene camphor, sulphur methyl benzylidene camphor, Terephthalidene Dicamphor Sulfonic Acid (therephthalidene dicamphor sulfonic acid) etc.;---cinnamate derivates, for example octyl methoxycinnamate (PARSOL

MCX), methoxy cinnamic acid ethoxyethyl group ester, diethanolamine methoxy cinnamate salt (diethanolaminemethoxycinnamate, PARSOL

Hydro), the methoxy cinnamic acid isopentyl ester, with the cinnamic acid derivative of siloxanes bonding;

---para-amino benzoic acid derivative, for example para-amino benzoic acid, ESCAROL 507 2-(ethyl hexyl) ester, N-oxypropylene groupization (N-oxypropylenated) parathesin, para-amino benzoic acid glyceryl ester.

---benzophenone, for example benzophenone-3, benzophenone-4,2,2 ＇, 4,4 ＇-tetrahydroxy-benzophenone, 2,2 ＇-dihydroxyl-4,4 ＇-dimethoxy benzophenone etc.;

--the ester of-benzylidene malonic acid, for example 4-methoxyl group benzylidene malonic acid two (2-ethylhexyl) ester;

--the ester of-2-(4-phenetidine methylene) propanedioic acid, 2-(the 4-phenetidine methylene) diethyl malonate of for example being put down in writing among the EP 0,895 776.

The organosilicone compounds of phenylmalonate ester---contain (benzmalonate) base is as EP0358584 B1, EP 0538431 B1 and EP 0709080 A1 record person;

---drometrizole trisiloxanes (drometrizole trisiloxane) (Mexoryl XL);

---pigment such as microgranular TiO ₂Deng." microgranular " means the about 5nm of granularity to about 200nm, and especially about 15nm is to the particle of about 100nm.TiO ₂Particle also can be coated with the metal oxide such as aluminum oxide or zirconium white, perhaps is coated with organic coating such as polyvalent alcohol, polymethyl siloxane (methicone), aluminum stearate, alkyl silane.These coating are well-known in this field.

---imdazole derivatives such as 2-Phenylbenzimidazole sulfonic acid and salt (PARSOL thereof

HS).The example of 2-Phenylbenzimidazole sulfonate for example is an alkali metal salt such as sodium salt or sylvite, ammonium salt, alkylbenzyldimethylasaltsum saltsum, primary amine salt, secondary amine salt and tertiary ammonium salt such as monoethanolamine salt, diethanolamine salt etc.

---salicylic acid ester derivative, for example Whitfield's ointment isopropyl benzyl ester, benzyl salicylate, butyl salicylate, octyl salicylate (NEO HELIOPAN OS), the different monooctyl ester of Whitfield's ointment or Uniderm Homsal (homosalate, HELIOPAN) etc.

---pyrrolotriazine derivatives, for example UVINUL T-150 (UVINULT-150), dioctyl amide-based small triazone (UVASORB HEB), two guoethol methoxyphenyl triazine (Tinosorb S) etc.

Wide spectrum or UV A sun-screening agent also are obtained the maximum absorption about 320 to 400nm material, and its example that is used in combination with The compounds of this invention that is considered for example is following organic compound and mineral compound:

---dibenzoylmethane derivative for example, the 4-tertiary butyl-4 '-methoxy dibenzoyl methane (PARSOL 1789), dimethoxy phenyl phenacyl ketone, isopropyl diphenyl formyl radical methane etc.;

---benzotriazole derivatives, for example 2,2 '-methylene radical-two-(6-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl)-phenol (TINOSORB M) etc.;

---phenylene-1,4-is two-benzoglyoxaline sulfonic acid or its salt, and for example 2,2-(1, the 4-phenylene) is two-(1H-benzoglyoxaline-4,6-disulfonic acid) (Neoheliopan AP);

The dihydroxy benaophenonel that---amino replaces, 2-(4-diethylamino-2-hydroxyl-benzoyl)-hexyl-benzoate for example is as the person of narrating among the EP 1046391;

---pigment such as microgranular ZnO or TiO ₂Deng." microgranular " means the about 5nm of granularity to about 200nm, and especially about 15nm is to the particle of about 100nm.This particle also can coat other metal oxides such as aluminum oxide or zirconium white, perhaps coats organic coating such as polyvalent alcohol, polymethyl siloxane (methicone), aluminum stearate, alkyl silane.These coating are well-known in this field.

Because the light stability of phenyl phenacyl ketone derivative is limited, thus available it desirably make the UV-A sun-screening agent Photostabilised.Therefore, " commonly used UV-A sun-screening agent " also means the phenyl phenacyl ketone derivative, for example with the PARSOL of following material stabilization

1789:

---3, the 3-diphenylacrylate is as the person of narrating among EP 0514491 B1 and EP 0780119 A1;

---benzylidene camphor derivative, as US 5,605, the person of narrating in 680;

---contain the phenylmalonic acid ester group organo-siloxane, as the person of narrating among EP 0358584 B1, EP0538431 B1 and EP 0709080 A1.

The present composition also contains habitual makeup adjuvant and additive; sanitas/antioxidant for example; fatty substance/oil; water; organic solvent; silicone; thickening material; tenderizer; emulsifying agent; auxiliary sun-screening agent; defoamer; wetting Agent for Printing Inks; spices; tensio-active agent; filler; sequestering agent; anionic polymer; cation type polymer; non-ionic polyalcohol or amphiphilic polymers or its mixture; propelling agent; souring agent or basifier; dyestuff; tinting material; pigment or nano-level pigment; especially those are suitable for covering the pigment that uv-radiation produces the additional light protective effect by physics mode; perhaps any other allocates the composition of makeup usually into, particularly is used for making the composition of shading/sunscreen composition.According to the product that will make, the auxiliary agent that those skilled in the art just can select to make up easily and dermatology is used and the expense of additive will be given among the application's the embodiment and illustrating, but be not limited to this.

Generally speaking, preferably add the antioxidant/sanitas of additional quantity.According to the present invention, allocate all known antioxidants of makeup usually into and all can use.Especially preferred is the antioxidant that is selected from following this class material: amino acid (for example; glycine; Histidine; tyrosine; tryptophane) and derivative; imidazoles (for example urocanic acid) and derivative; peptide (D for example; the L-carnosine; the D-carnosine; L-carnosine and derivative such as anserine); carotenoid; carotene (alpha-carotene; β-Hu Luobusu; Lyeopene) and derivative; chlorogenic acid and derivative; Thioctic Acid and derivative (for example Thioctic acid, dihydro-); aurothioglucose; propyl deracil and other mercaptan (Trx for example; gsh; halfcystine; Gelucystine; cystamine and glycosyl thereof; the N-ethanoyl; methyl; ethyl; propyl group; amyl group; butyl and lauryl; palmityl; oil base; y-18 carbon dialkylenes (y-linoleyl); cholesteryl and glyceryl ester) and salt; Tyox B; thio-2 acid distearyl ester; thio-2 acid and derivative (ester thereof; ether; peptide; lipoid; Nucleotide; nucleosides and salt) and sulphur oxygen imido (sulfoximine) compound of very low compatible dosage (for example pmol/kg to μ mol/kg) (S-(the amino 3-carboxylic of 3-propyl group)-S-butyl sulphur oxygen imido (buthionine sulfoximine) for example; homocysteine sulphur oxygen imido; S-(the amino 3-carboxylic of 3-propyl group)-S-butyl sulfone (buthionine sulfone); five-; six-; seven thionines (thionine) sulphur oxygen imido), also has (metal) sequestrant (alpha-hydroxy fatty acid for example in addition; palmitinic acid; phytinic acid; lactoferrin); beta-hydroxy acid (citric acid for example; lactic acid; oxysuccinic acid); humic acid; gallic acid; Galla Chinensis extract; bilirubin; uteroverdine; EDTA; EGTA and derivative thereof; unsaturated fatty acids and derivative thereof (gamma-linoleic acid for example; linolic acid; oleic acid); folic acid and derivative thereof; ubiquinone and ubiquinol (ubiquinol) and derivative thereof; vitamins C and derivative (for example Quicifal and xitix four different cetylates; Mg-ascorbic acid phosphoric acid esters (Mg-ascorbyl phosphate); the Na-ascorbic acid phosphoric acid esters; the xitix acetic ester)); vitamin-E and derivative (for example VITAMIN-E-acetic ester); the mixture of natural VE; vitamin A and derivative (VITAMIN-A-cetylate and VITAMIN-A-acetic ester) and coniferyl benzoic ether; rutinic acid and derivative; the alpha-glycosyl violaguercitrin; forulic acid; the furfurylidene sorbitol; carnosine; butylhydroxy toluene; butylated hydroxy anisole; trihydroxybutyrophenone (trihydroxybutyrophenone); urea and derivative thereof; seminose and derivative; zinc and derivative (ZnO for example; ZnSO ₄), the suitable derivative (salt, ester, ether, sugar, Nucleotide, nucleoside, peptide and lipoid) of selenium and derivative (for example selenomethionine), stilbene and derivative (for example stilbene oxide compound (stilben oxide), trans-the stilbene oxide compound) and above-mentioned each activeconstituents.Be as the criterion in present composition gross weight, one or more sanitas/antioxidants can the extremely amount existence of about 10% (weight) of about 0.01% (weight).Preferably, one or more sanitas/antioxidants can the extremely amount existence of about 1% (weight) of about 0.1% (weight).

Generally, also contain surface active ingredient in the prescription such as emulsifying agent, solubilizing agent etc.Emulsifying agent can make two or more component uniform mixing that do not dissolve each other.And emulsifying agent also plays a part stable composition.Among the present invention, for forming O/W, W/O, O/W/O, W/O/W type emulsion/microemulsion, the emulsifying agent that may use comprises sorbitan oleate, sorbitan sesquioleate, sorbitan isostearate, the anhydrosorbitol trioleate, polyglyceryl (polyglyceryl)-3-diisopstearate, the poly glycidyl ester of oleic acid/Unimac 5680, polyglyceryl-6 six ricinoleate (hexaricinolate), polyglyceryl-4-oleic acid ester, polyglyceryl-4 oleic acid esters/PEG-8 propylene glycol cocounut oil ester (cocoate), oleoyl glycol amines (DEA), trolamine (TEA) myristinate, the TEA stearate, Magnesium Stearate, sodium stearate, potassium laurate, ricinoleic acid potassium, cocinic acid sodium (sodium cocoate), tallow acid (tallowate) sodium, castoric acid (castorate) potassium, sodium oleate, and composition thereof.Other suitable emulsifying agent is phosphoric acid ester and salt thereof, for example phosphoric acid n-Hexadecane ester (

A), diethanolamine n-Hexadecane phosphoric acid ester ( ), the n-Hexadecane potassiumphosphate ( K), olein sodium phosphate (sodium glyceryl oleate phosphate), hydrogenated vegetable glyceryl ester phosphoric acid ester and composition thereof.In addition, one or more synthetic polymers can be used as emulsifying agent.For example, PVP eicosylene (eicosene) multipolymer, acrylate/C _10-30Alkyl acrylate cross-linked polymer (crosspolymer), acrylate/stearic alcohol ether (steareth)-20 alkylmethacrylate polymer, PEG-22/ dodecyl diol copolymer, PEG-45/ dodecyl diol copolymer, and composition thereof.Preferred solvent be the phosphoric acid cetyl ester (

A), hexadecyl di(2-ethylhexyl)phosphate ethanolamine salt (

), potassium cetyl phosphate ( K), PVP eicosylene multipolymer, acrylate/C _10-30-alkyl acrylate cross-linked polymer, PEG-20 sorbitan isostearate, sorbitan isostearate and composition thereof.Total amount of one or more emulsifying agents is about 0.01wt%～about 20wt% of present composition total amount.Preferably, use the emulsifying agent of about 0.1wt.%～about 10wt.%.

Lipoid can advantageously be selected from mutually:

Mineral oil and mineral wax;

Oil is capric acid (caprinic acid) or sad triglyceride level for example, preferred Viscotrol C;

Oil or wax and other natural or synthetic oil, in a preferred embodiment, lipid acid and alcohol, the ester of for example ester of Virahol, propylene glycol, glycerine, or Fatty Alcohol(C12-C14 and C12-C18) and carbonic acid or lipid acid;

Phenylformic acid alkyl ester; And/or

Silicone oil is dimethyl polysiloxane, diethyl polysiloxane, phenylbenzene polysiloxane, cyclomethicone (cyclomethicone) and composition thereof for example.

Can add exemplary fatty substance in the oil phase of emulsion of the present invention, microemulsion, oleogel, water dispersion or fatty dispersion and advantageously be selected from the alkyl carboxylic acid of saturated and/or unsaturated, straight chain or branching, 3～30 carbon atoms, with the ester of the alcohol of saturated and/or unsaturated, straight chain and/or branching, 3～30 carbon atoms, and the ester of the alcohol of aromatic carboxylic acid and saturated and/or unsaturated, straight chain or branching, 3-30 carbon atom.This kind ester can advantageously be selected from Wickenol 155, octyl group cocounut oil acid esters (cocoate), the Unimac 5680 monooctyl ester, Wickenol 142, the different pelargonate of 16/octadecyl (cetearyl), the tetradecanoic acid isopropyl esters, the palmitinic acid isopropyl esters, the stearic acid isopropyl esters, the oleic acid isopropyl esters, stearic acid just-butyl ester, lauric acid just-polyhexamethylene, oleic acid just-last of the ten Heavenly stems ester, the stearic acid isooctyl acrylate, the different nonyl ester of stearic acid, the different nonyl ester of different n-nonanoic acid, palmitinic acid 2-(ethyl hexyl) ester, lauric acid 2-(ethyl hexyl) ester, stearic acid 2-hexyl ester in the last of the ten Heavenly stems, palmitinic acid 2-octyl group dodecyl ester, the enanthic acid stearyl, oleic acid oil base ester, erucic acid oil base ester, oleic acid erucyl ester (erucyloleate), erucic acid erucyl ester, stearic acid tridecyl ester, the tridecyl trimellitate, with synthesizing of these esters, half-synthetic or natural mixture, for example Jojoba oil.

Other is applicable to that the lipid fraction of preparation of the present invention comprises polar oil (polar oils) for example Yelkin TTS (lecithin) and fatty acid triglycercide, be saturated and/or undersaturated, straight chain or branching, 8～24 carbon atoms, the triglyceride level of the carboxylic acid of preferred 12～18 carbon atoms, wherein fatty acid triglycercide is preferably selected from synthetic, semi-synthetic or natural oil (coconut oil glyceryl ester (cocoglyceride) for example, sweet oil, wunflower seed oil, soya-bean oil, peanut oil, rape seed oil, sweet almond oil, plam oil, Oleum Cocois, Viscotrol C, hydrogenated castor oil, wheat oil, wine stone oil, Queensland nut oil and other); Polar oil is for example mineral oil, Vaseline (vaseline) of straight chain and/or branched hydrocarbon and wax for example; Paraffin, squalane (squalane) and squalene (squalene), polyolefine, Parleam and isohexadecane, preferred polyolefine is a poly decene; Dialkyl ether, for example two decoyl ethers; The for example preferred cyclomethicone (cyclomethicone) (octamethylcyclotetrasiloxane) of straight chain or ring-type silicone oil, hexadecyl polydimethylsiloxane (cetyldimethicone), hexamethyl cyclotrisiloxane, polydimethylsiloxane, poly-(methylphenyl siloxane) and composition thereof.

Other lipid fraction that can advantageously add in the preparation of the present invention comprises Isoeicosane (isoeikosane), neopentyl glycol two heptanoates, propylene glycol dicaprylate/dicaprate, caprylic/capric/two glyceryl succinates, butyleneglycol octanoate/decylate, C _12-13-alkyl lactate ester, two C _12-13-alkyl tartrate, three Tegin ISOs, Dipentaerythritol six octanoates/six decylates, Propylene glycol monoisostearate, tricaprylin, Isosorbide dimethyl ether (dimethylisosorbid).Especially preferably use C _12-15The mixture of-alkyl benzoate and 2-ethyl-hexyl isostearate, C _12-15The mixture of-alkyl benzoate and the different pelargonate of isotridecyl, and C _12-15The mixture of-alkyl benzoate, 2-ethylhexyl isostearate and the different pelargonate of isotridecyl.

The oil phase of preparation of the present invention also contains for example wax of beeswax, Chinese wax (chinawax), rheum officinale beeswax and other insect of natural phant or animal wax, and shea butter and theobroma oil.

Can sneak into wetting Agent for Printing Inks in the present composition, to keep hydration or to make skin rehydration.By being provided, protective layer prevents that sealing is called softener from the moistening agent of skin evaporation.Additional softener provides softening or the skin moisten effect to skin surface, and to be considered to usually topical application be safe.Preferred softener comprises mineral oil, lanolin, vaseline, capric acid (capric) triglycerin aldehyde, sad triglycerin aldehyde, cholesterol; Siloxanes, for example polydimethylsiloxane, cyclomethicone; Prunus amygdalus oil, Jojoba oil, Lipoval A, Viscotrol C, sesame oil, wunflower seed oil, Oleum Cocois and wine stone oil, theobroma oil, sweet oil, Aloe extract (aloe extracts); Lipid acid, for example oleic acid and stearic acid; Fatty Alcohol(C12-C14 and C12-C18), for example hexadecanol and hexadecyl alcohol; Hexanodioic acid diisopropyl ester, hydroxybenzoate, C _9-15The different nonyl ester of benzoic ether, different n-nonanoic acid of-alcohol; Ether, for example polyoxypropylene butyl ether and polyoxypropylene cetyl ether, C _12-15-alkyl benzoate, and composition thereof.Most preferred softener is hydroxybenzoate, Aloe vulgaris (aloe vera), C _12-15-alkyl benzoate, and composition thereof.Softener can exist with the amount of about 1wt%～about 20wt% of total composition.The amount of softener is preferably about 2wt%～about 15wt%, most preferably from about 4wt%～about 10wt%.

With the water bonded, therefore, the moistening agent that holds it in skin surface is called wetting Agent for Printing Inks.The suitable wetting Agent for Printing Inks that can join in the present composition is, for example glycerine, polypropylene glycol, polyoxyethylene glycol, lactic acid, pyrrolidone carboxylic acid (pyrrolidon carboxylic acid), urea, phosphatide (phopholipids), collagen protein, elastin, ceramide, Yelkin TTS Sorbitol Powder, PEG-4, and composition thereof.The polymkeric substance moistening agent that other suitable moistening agent is a lower class: water-soluble and/or swellable and/or with the polysaccharide of water-setting gel, the polysaccharide of hyaluronic acid, chitosan and/or rich Fucose for example, it is for example conduct

1000 (CAS-Nr.178463-23.5) obtain from SOLABIA S.Randomly with about 0.5wt%～about 8wt% of the present composition, the amount of preferably about 1wt%～about 5wt% exists one or more wetting Agent for Printing Inkss.

The water of the present composition can contain common cosmetics additive, for example pure, especially lower alcohol, preferred alcohol and/or Virahol, lower glycol or polyvalent alcohol and ether thereof, preferred propylene glycol, glycerol, ethylene glycol, ethylene glycol monomethyl ether or single-butyl ether, propylene glycol monomethyl ether or single ethyl ether or single-butyl ether, glycol ether monomethyl ether or single-butyl ether, propylene glycol monomethyl ether or single ethyl ether or single-butyl ether, glycol ether monomethyl ether or single ethyl ether and analogous products, polymkeric substance, suds-stabilizing agent; Ionogen and one or more thickening materials especially.The thickening material that can be used in the preparation of the present invention, helps to produce suitable product denseness comprises acrylate copolymer (carbomer), silicon-dioxide, magnesium and/or aluminosilicate, beeswax, stearic acid, Stearyl alcohol polysaccharide and derivative thereof, for example xanthan gum, hydroxypropylcellulose, polyacrylamide, acrylate cross linked polymkeric substance, preferred acrylate copolymer, 980,981,1382,2984,5984 for example independent type carbopole

Or its mixture.Can be included in the present composition with in and the suitable neutralizing agent of component (for example emulsifying agent or frothing aid (foambuilder)/stablizer) include but not limited to hydroxide bases (alkali hydroxide), for example sodium hydroxide and potassium; Organic bases, for example diethanolamine (DEA), trolamine (TEA), amino methyl propyl alcohol and composition thereof; Amino acid is arginine and Methionin for example, and any aforesaid combination.The amount of neutralizing agent can be about 0.01wt%～about 8wt% of the present composition, preferred 1wt%～about 5wt%.

Adding the ionogen in the present composition, perhaps is that the behavior of change hydrophobic emulsifying agent is necessary.Therefore, the emulsion/microemulsion among the present invention can preferably contain a kind of ionogen of or several salt, comprising negatively charged ion such as chlorion, sulfate radical, carbonate, borate and aluminate, but is not limited to these.Other suitable ionogen can organic anion be the basis, such as, but be not limited to, lactic acid salt, acetate, benzoate, propionic salt, tartrate and Citrate trianion.Positively charged ion is preferably selected ammonium, alkylammonium, basic metal or alkaline-earth metal, magnesium ion, iron ion or zine ion.Particularly preferred salt is Repone K and sodium-chlor, sal epsom, zinc sulfate and composition thereof.In the present composition, the amount that ionogen can exist is that about 0.01% (weight) is to about 8% (weight).

Cosmetic composition of the present invention can be used as and is used to prevent people's epidermis or the composition that hair is subjected to ultraviolet damage, as barrier compositions.Particularly, this composition can emulsion, the form of thickening emulsion, gel, cream, emulsion, ointment, powder or solid tubular rods (solid tube stick) provides, and can pack with aerosol form on demand, also can mousse, foaming agent or spray form provide.When make-up composition of the present invention was not subjected to ultraviolet radiation or is used as barrier compositions for the protection human epidermal, said composition can be taked to suspend or be scattered in the suspension in solvent or the fatty substance, the form of dispersion; Perhaps as the form (specifically, O/W or w/o type, O/W/O or W/O/W type) of selecting to take emulsion or microemulsion, for example cream or emulsion, vesicular dispersion; Take ointment, gel, pipe dress solid bar form or aerosol mouse form.Emulsion also can contain anionic, non-ionic type, cationic or amphoteric surfactant.

The compounds of this invention protection skin and hair are not subjected to the UV-A radiation hazradial bundle.These compounds can be replenished by other UV-A sun-screening agents in the organic phase, thereby produce higher sun-proof result.These compounds can easily be sneaked in the different make-up compositions, and these compounds demonstrate more long wavelength's protection than other known UV-sun-screening agents, and demonstrate more long wavelength's protection than other commercially available water miscible UV-A sun-screening agents especially, thereby be effective UV-A lightscreening agent, rather than UV-A/UV-B gap lightscreening agent (gapfilter), and protecting skin is not painted by visible light.In addition; the remarkable advantage of new compound is shown in the general formula (I); these compounds present higher dullness than known other water-soluble UV-A sun-screening agents, and especially have than existing commercially available water-soluble UV-A sun-screening agent even better dullness, thereby produce better protection.Compound shown in the general formula (I) also presents excellent light stability.Be unexpectedly, the compound shown in the general formula (I) also makes emulsion-stabilizing, thereby can be used as the assistant for emulsifying agent of the present composition, if these compounds are taked emulsion form.Compound shown in the general formula (I) presents very low percutaneous permeation, and skin and hair are had good clinging power.

Provide the following example further to illustrate method and composition of the present invention.These embodiment only are exemplary, in no case are intended to limit protection scope of the present invention.

Embodiment 1

4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group-oxyethyl group phosphoric acid ester one sodium salt):

A) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group-ethanol)

350ml three neck reaction flasks are equipped with thermometer, reflux exchanger and have the oil bath of magneton agitator, dress (is pressed Helv.Chim.Acta 1962 with the 4-dicyano methylene radical-4H-pyrans that is present in the 30.1g (175mmol) in the 150ml propyl carbinol in the flask, 1908-1917 prepares) and 20.2g (192mmol) 2-(2-amino ethoxy)-ethanol (Fluka), and under argon atmospher, heated 90 minutes.After the cooling, whole suspension are filtered, with ethyl acetate, Di Iso Propyl Ether and pentane washing filter residue, get the little tawny crystal of 20.3g after the drying successively.157～158 ℃ of fusing points, UV (THF) 360 and 372nm (32 ' 332).

B) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group-oxyethyl group phosphoric acid ester one sodium salt)

750ml four neck reaction flasks are equipped with thermometer, dropping funnel, reflux exchanger, pH electrode and have the cooling bath of magneton agitator, under argon atmospher, dress is to be present in prepared 4-dicyano methylene radical-2 above the 19.5g (75mmol) among the 250mlTHF in the flask, 6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group-ethanol) and 13.6ml (97.5mmol) triethylamine (Fluka) also are chilled to 10 ℃.Then, in 15 minutes, add the POCl that 13.8g (90mmol) is dissolved in 50mlTHF with dropping funnel ₃Stirred the mixture under the room temperature 16 hours, and followed the tracks of reaction, filtering throw out, the NEt that is generated to remove with HPLC ₃* HCl.Filtrate is chilled to 10 ℃ again, and adds the hexaoxacyclooctadecane-6-6 of 1mg, add the 2.0-n NaOH aqueous solution of 97.5ml then, check pH simultaneously.Restir reactant 90 minutes, and under 20 ℃, add the 2.0-n NaOH aqueous solution again, reach till 4 until pH.This moment, isolate water, and wash it with the 100ml ethyl acetate.Add the saturated NaCl aqueous solution of 50ml, so that the product precipitation, and it can be filtered out, again with the 200ml washing with acetone it.Get the 18.2g clear crystal after the drying.Solubleness 168g/l in the water.This salt of recrystallization in DMF.158～159 ℃ of fusing points; UV (water) 350nm (E=979).According to Berset et al., Internat.J. Cosmetic Science 18:167-177 (1996) is with 7: 3 water/glycerol mixture solution light stability of this salt of having made liquid phase measuring.Find that product has light stability.

Embodiment 2

4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group sulfuric ester one sodium salt):

A) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-second-2-alcohol

350ml three neck reaction flasks are equipped with thermometer, reflux exchanger and have the oil bath of magneton agitator, dress (is pressed Helv.Chim.Acta 1962 with 25.8g (150mmol) the 4-dicyano methylene radical-4H-pyrans that is present in the 100ml thanomin (Fluka) in the flask, the 1908-1917 preparation), and under argon atmospher, be heated to 80 ℃, kept 30 minutes.Soon just observe thermopositive reaction after the reaction beginning.After the cooling,, and give filtration with 100ml propyl carbinol diluted mixture thing.Use 2 * 10ml cold water and 2 * 100ml washing with acetone filter residue successively.Get the little yellow crystals of 17.5g after the drying.267～268 ℃ of fusing points, UV (THF) 360 and 372nm (26 ' 305).

B) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group sulfuric ester one sodium salt)

The 100ml reaction flask is equipped with agitator, reflux exchanger, thermometer, oil bath and argon atmospher, dress is to be present in the above-mentioned 4-dicyano of 2.15g (10mmol) methylene radical-2 in 9: 1 acetonitrile/pyridine mixtures of 30ml in the flask, 6-dimethyl-1, the 4-dihydropyridine-pure and mild 1.91g of N-second-2-(12mmol) sulphur trioxide-pyridine recombiner (Fluka).Violent stirring limit, limit keeps this mixture heating up to 60 ℃ 30 minutes.After 10 minutes, just in fact detect less than starting raw material with HPLC.Under the room temperature,, and filter it with this mixture of 30ml acetone diluted.With acetone, diisopropyl ether and pentane washing filter residue, get 3.1g clear crystal, 209～210 ℃ of fusing points after the drying.This material is dissolved in the 30ml water.Add the 1 normal 1-n NaOH aqueous solution, and stirred the mixture 15 minutes, and in rotary evaporator (rotavap), carry out high vacuum and concentrate.In filter residue, add 50ml water again, and as above concentrate.Repeat this process again 2 times, smell flavor until can't smell pyridine.Again dry substance is dissolved in 5 times in the water of its weight, adds 200mlTHF and make it precipitation, filter and with THF and washing with acetone residue, must the 2.9g clear crystal.198 ℃ of fusing points (decomposition); UV (water) 352nm (E=1261).Solubleness 〉=25g/l in the water.According to Berset et al., Internat.J.CosmeticScience18:167-177 (1996) is with 7: 3 water/glycerol mixture solution light stability of this product of having made liquid phase measuring.Find that this product has light stability.

Embodiment 3

4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-[3-(N, N-dimethyl)-N-(oxyethyl group-ethoxy ethanol-yl)-propyl group-ammonium iodide]

A) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-(3-[N, N-dimethylamino]-propane)

250ml three neck reaction flasks are equipped with thermometer, reflux exchanger and have the oil bath of magneton agitator, dress (is pressed Helv.Chim.Acta1962 with 14.5g (82.2mmol) the 4-dicyano methylene radical-4H-pyrans that is present in the 145ml propyl carbinol in the flask, 1908-1917 prepares) and 10.1g (99mmol) 3-(N, the N-dimethylamino)-propylamine (Fluka), and under argon atmospher, heated 2 hours.After the cooling, filtering suspension liquid with cold propyl carbinol washing filter residue, gets the little yellow crystals of 10.4g after the drying.187～188 ℃ of fusing points.UV (ethanol) 360nm (37 ' 287).

B) 2-[2-(2-iodo oxyethyl group)-oxyethyl group]-ethanol

The 25ml reaction flask is equipped with reflux exchanger, oil bath and magneton agitator, and dress is to be present in 2g (11.9mmol) 2-[2-(2-chloro the oxyethyl group)-oxyethyl group in the 20ml acetone in the flask]-ethanol (Fluka), 4g sodium iodide and 3g sodium bicarbonate.Reaction mixture refluxed is spent the night, filtered after cold.Filtrate is concentrated rotary evaporator, is dissolved in 5ml CH ₂Cl ₂After give filtration again.Then, concentrated filtrate in rotary evaporator gets the 2.5g yellow oil again.NMR confirms pure material (CDCl ₃) 2.58 s wide (1H/OH); 3.22 t (2H/CH ₂-J); 3.53-3.77m (10H/CH ₂-O).

C) 4-dicyano methylene radical-2,6-dimethyl-1,4-dihydropyridine-N-[3-(N, N-dimethyl)-N-(oxyethyl group-ethoxy ethanol-yl)-propyl group-ammonium iodide]

The 50ml reaction flask is equipped with reflux exchanger, oil bath and magneton agitator, dress is to be present in the as above made 4-dicyano of 1.28g (5mmol) methylene radical-2 among the 15mlDMF in the flask, 6-dimethyl-1,4-dihydropyridine-N-(3-[N, N-dimethylamino]-propane), the above-mentioned 2-[2-of 1.34g (5.5mmol) (2-iodo oxyethyl group)-oxyethyl group]-ethanol.Reaction mixture refluxed is spent the night, and show no starting raw material with TLC.Concentrated reaction mixture in rotary evaporator carries out high vacuum (HV) drying subsequently.With hexanaphthene wash residual thing, wash it with ethyl acetate again, then recrystallization in ethanol.Get the 2.09g brown crystal.130～180 ℃ of fusing points (decomposition); UV (ethanol) 362nm (37 ' 946).

Embodiment 4

1-{2-[2-(4-dicyano methylene radical-2,6-dimethyl-4H-pyridine-1-yl)-oxyethyl group]-ethyl }-pyridine-N-oxide

A) 2-{1-[2-(2-chloro-oxyethyl group)-ethyl]-2, the inferior pyridin-4-yl of 6-dimethyl-1 H-}-propane dinitrile

750ml four neck reaction flasks are equipped with thermometer, dropping funnel, reflux exchanger, have the cooling heating bath of magneton agitator, under argon atmospher, dress is to be present in prepared 4-dicyano methylene radical-2 above the 19.5g (75mmol) among the 50ml THF in the flask, 6-dimethyl-1,4-dihydropyridine-N-(oxyethyl group-ethanol) (embodiment 6.1.a) and trace of triethylamine (Fluka) also are chilled to 10 ℃.Then, in 15 minutes, add the SOCl that 10.7g (90mmol) is dissolved in 50ml THF with dropping funnel ₂Solution.Stirred the mixture under the room temperature 1 hour, reflux is 4 hours then.Follow the tracks of reaction with HPLC.Mixture is inclined on ice, is leached product, and in ethyl acetate recrystallization.Get white crystal, 148～149 ℃ of fusing points.

B) 1-{2-[2-(4-dicyano methylene radical-2,6-dimethyl-4H-pyridine-1-yl)-oxyethyl group]-second

A) 2-[1-(3-hydroxyl-phenyl)-2, the inferior pyridin-4-yl of 6-dimethyl-1H-}-propane dinitrile

The 10ml reaction flask is equipped with reflux exchanger, magneton agitator and oil bath, under argon atmospher, 0.86g (5mmol) 4-dicyano methylene radical-4H-pyrans pack in the flask into (according to Helv.Chim.Acta1962,1908-1917 prepares) and 2.8g (25mmol) 3-amino-phenol (Fluka), and be heated to 140 ℃, kept 5 hours.While hot reaction mixture is poured among the 2n HCl of 100ml, and with twice of 100ml ethyl acetate extraction.Organic phase merges the back with 2n HCl back scrubbing, is concentrated in rotary evaporator and drying.The gained crystal washs with warm ethyl acetate and MeOH, and after drying, gets the 460mg white crystal.Fusing point〉300 ℃, TLC (EtOAc on the silica gel: Rf=0.15 hexane=1: 1).

B) 3-[3-(4-dicyano methylene radical-2,6-dimethyl-4H-pyridine-1-yl)-phenoxy group] propane-1-sulfonic acid

50ml three neck reaction flasks are equipped with thermometer, reflux exchanger, magneton agitator and add hot radical }-pyridinium chloride

The 50ml reaction flask is equipped with reflux exchanger, heating bath and magneton agitator, under argon atmospher, dress is to be present in the above-mentioned 2-{1-[2-of 1.4g (5mmol) (2-chloro-the oxyethyl group)-ethyl in the 25ml pyridine in the flask]-2, the inferior pyridin-4-yl of 6-dimethyl-lH-}-propane dinitrile, reflux 5 hours.Generate thick suspension, it is leached, and, wash with THF again with a small amount of cold pyridine washing.After the drying, get the 1.69g microlite, 248～251 ℃ of fusing points (decomposition), UV (water) 352nm (E=1149).Solubleness in the water〉〉 200g/l.

Embodiment 5

3-[3-(4-dicyano methylene radical-2,6-dimethyl-4H-pyridine-1-yl)-and phenoxy group] propane-1-sulfonic acid bath, under argon atmospher, dress is to be suspended in the above-mentioned 2-[1-of 263mg (1mmol) (3-hydroxyl-phenyl)-2 in anhydrous THF of 20ml and the 0.1ml dry DMF mixture, the inferior pyridin-4-yl of 6-dimethyl-1H-in the flask]-propane dinitrile and 26.5mg (1.05mmol) anhydrous Na H (95%).Observing hydrogen produces.After 45 minutes, with 1 of 134mg (1.1mmol), 3-N-morpholinopropanesulfonic acid lactone (propan sultone) adds in the suspension, and reaction mixture is heated to 70 ℃, keeps 5 hours, follows the tracks of with HPLC.Take advantage of cold filtering mixt, residue washs with a small amount of THF, gets the 260mg white powder.At MeOH/CH ₂Cl ₂Middle recrystallization is used CH ₂Cl ₂Washing crystal also gives drying, gets the 190mg clear crystal, 200 ℃ of fusing points (decomposition).UV (water) 352nm (E=1150), solubleness in the water〉50g/l.

Embodiment 6

The preparation of O/W type ultra light sun block lotion UV-B and UV-A

The wide spectrum ultra light sun block lotion that contains 2% embodiment, 1 made compound

The A part is heated to 85 ℃ in reactor.The B part slowly added in 10 minutes, then added KOH, with the emulsion cooling and the degassing.

Embodiment 7

The sun-proof emulsion of water-resisting type

Embodiment 8

The spray-type ultra light sun block lotion

	Composition	The INCI nomenclature		% (weight)
					A)	PARSOL MCX	Ethylhexyl methoxy cinnamate	1)	6.00
	PARSOL 5000	4 methyl benzylidene camphor	1)	2.00
						Emulgade SE-PE	Stearin, 16/Stearyl alcohol polyoxyethylene (20) ether, 16/Stearyl alcohol polyoxyethylene (12) ether, 16/Stearyl alcohol, palmitinic acid hexadecyl ester mixture	2)	7.00
	Eumulgin B-2	16/octodecyl alcohol polyoxyethylene (20) ether	2)	6.00
						MVritol 318	(caprylic/capric) triglyceride level	2)	3.00
	Cetiol A	Lauric acid hexyl ester	2)	6.00
						Silicone DC 345 fluids	Cyclomethicone	6)	7.00
	Antaron V-220	PVP/ eicosylene multipolymer	7)	2.00
						Edeta BD	The EDTA disodium salt	3)	0.10
	Yoshinox BHT	BHT	5)	0.05
						Phenonip	Phenoxyethyl alcohol, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propylparaben and butyl p-hydroxybenzoate	8)	0.60
					B)	Deionized water	Water		q.s.100

	Composition	The INCI nomenclature		% (weight)
						Glycerine	Glycerine	5)	5.00
					C)	PARSOL HS	Phenylbenzimidazolesulfonic acid	1)	2.00
	The product of embodiment 2			2.00
						Deionized water	Water		20.00

KOH 10％sol.

Potassium hydroxide

4.40

Operation steps:

While stirring with A) partly be heated to 85 ℃.After stirring, stir and add B down) partly (80 ℃).Then, stir and add C down) partly (40 ℃) (guarantee that Parsol HS dissolves fully, if residual trace then adds small amount of alkali to be neutralized, until solution clarification, pH〉7).At last, pH regulator to being at least 7, and is chilled to room temperature.

The supplier:

1)DSM Nutritional Products，CH-4002 Basel/Switzerland

2)COGNIS，D-40551 Düsseldorf/Germany

3)BASF AG， D-67056 Ludwigshafen/Germany

4)GOODRICH COMPANY，Cleveland-OH 44141-3247/USA

5)FLUKA CHEMIE AG，CH-9471 Buchs/Switzerland

6)DOW CORNING CORP.，Midland-Mi 48686-0994/USA

7)ISP TECHNOLOGIES INC.，Wayne-NJ 07470/USA

8)NIPA LABORATORIES LTD，Mid Glam.-CF38 2SN/England

Embodiment 9

O/W VITAMIN type wide spectrum ultra light sun block lotion

	Composition	The INCI nomenclature		% (weight)
					A)	PARSOL MCX	2-Ethylhexyl cinnamate	1)	4.00
	PARSOL 1789	Butyl methoxyl group dibenzoyl methane	1)	1.00
						PARSOL 5000	4 methyl benzylidene camphor	1)	3.50
	Estol GMM 3650	Myristin	8)	4.00

	Composition	The INCI nomenclature		% (weight)
						Cetyl alcohol	Cetyl alcohol		2.00
	Ganex V-220	PVP/ eicosylene multipolymer	4)	2.00
						Tegosoft TN	Phenylformic acid C 12-15Alkyl ester	5)	10.00
	Myritol 318	(caprylic/capric) triglyceride level	6)	6.00
						Yoshinox BHT	BHT		0.05
	Edeta BD	The EDTA disodium	2)	0.10
						Phenonip	Phenoxyethyl alcohol, P-hydroxybenzoic acid first	3)	0.60

		Ester, ethyl p-hydroxybenzoate, propylparaben and butyl p-hydroxybenzoate
						AMPHISOL K	Potassium cetyl phosphate	1)	2.00
	VITAMIN EACETATE	VITAMIN E ACETATE	1)	2.00
					B)	Deionized water	Water		ad 100
	Propylene glycol	Propylene glycol		5.00
						Carbopol 981(1％sol.)	Acrylate copolymer	7)	10.00
	D-PANTHENOL75L	Panthenol	1)	2.70
C)	KOH(10％sol.)	Potassium hydroxide		0.70
D)	Deionized water	Water		20.00

		Ester, ethyl p-hydroxybenzoate, propylparaben and butyl p-hydroxybenzoate
						The product of embodiment 2			2.00
	PARSOL HS	Phenylbenzimidazolesulfonic acid	1)	2.00
						KOH 10％sol.	Potassium hydroxide		4.40

Operation steps:

While stirring with A) partly be heated to 85 ℃.After stirring, stir the B that is added on 75 ℃ of preheatings down) part and C) partly to 75 ℃.Add and be preheating to 75 ℃ D) partly (guarantee that Parsol HS dissolves fully) if residual trace then adds small amount of alkali and neutralized, until the solution clarification.Homogenized 30 seconds with 11000 rev/mins speed.Be chilled to room temperature.

Physical data:

pH：7.20

Viscosity (Brookfield RVT, 25 ℃, 6,10 rev/mins of rotors): about 12350cP

SPF: in vivo test 5 tested objects, LaboratoireDermscan, Lyon Ref.98098 (02.98) by the Colipa agreement

The supplier:

9)ROCHE VITAMINS LTD，CH-4070 Basel/Switzerland

10)BASF AG，D-67056 Ludwigshafen/Germany

11) NIPA LABORATORIES LTD，Mid Glam.-CF38 2SN/England

12)ISP TECHNOLOGIES INC.，Wayne-NJ 07470/USA

13)GOLDSCHMIDT AG，D-45127/Germany

14)COGNIS，D-40551Düsseldorf/Germany

15) B.F.GOODRICH COMPANY；Cleveland-OH44141/USA

16) UNICHEMA CHEMIE GmbH，D-46446 Emmerich/Germany

Claims (22)

1. the compound shown in the general formula I

In the formula,

R ¹And R ²For-CN;

R ³, R ⁴, R ⁵And R ⁶Be independently selected from hydrogen atom or C ₁-C ₁₀Alkyl,

X is for containing 1 to 20 carbon atom and optional 1 to 10 heteroatoms, and contains the alkyl of the group of at least one lotus positive electricity or bear electricity, and

Y is counter ion.

2. the described compound of claim 1, wherein X is for containing 1 to 20 carbon atom and optional 1 to 10 heteroatoms, and contains alkyl, alkaryl or the alkyl-cycloalkyl of the group of at least one lotus positive electricity or negative charge.

3. the described compound of claim 2, wherein X is C ₁-C ₁₀Alkylidene group, the optional group that contains 1 to 10 heteroatoms and comprise at least one lotus positive electricity or negative charge of this alkylidene group.

4. any one described compound in the claim 1 to 3, wherein X contains 1 to 6 heteroatoms.

5. the described compound of claim 4, wherein heteroatoms is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom and phosphorus atom.

6. any one described compound in the claim 1 to 5, wherein positive charge of the group band of lotus positive electricity or bear electricity.

7. the described compound of claim 6, wherein the group of lotus positive electricity or bear electricity is a quaternary ammonium group.

8. the described compound of claim 7, wherein Y is a halide-ions.

9. any one described compound in the claim 1 to 5, wherein negative charge of the group band of lotus positive electricity or bear electricity.

10. the described compound of claim 9, wherein the group with a negative charge is selected from-COO ^-,-O-SO ₃ ^-With-O-PO ₃H ^-

11. the described compound of claim 10, wherein Y is alkalimetal ion, alkaline-earth metal ions, triethanol ammonium ion, amino methyl propyl alcohol ion or trometamol ion.

12. any one described compound, wherein R in the claim 1 to 11 ³And R ⁴The group hydrogen atom of respectively doing for oneself.

13. any one described compound, wherein R in the claim 1 to 12 ⁵And R ⁶Group is independently selected from hydrogen atom and C ₁-C ₆Alkyl.

14. any one described compound, wherein R in the claim 1 to 13 ¹And R ²Group is cyano group.

15. the described compound of claim 1, promptly

16. contain the UV-A shading composition of any one compound that defines in the claim 1 to 15.

17. the described UV-A shading composition of claim 16, said composition are the make-up compositions that is used for protecting skin or the anti-UV-A irradiation of hair.

18. claim 16 or 17 described UV-A shading compositions, said composition comprises one or more additional sun-screening agents, and these sun-screening agents are selected from particulate pigment and polymer class UV screening agent.

19. the described UV-A shading composition of claim 18, particulate pigment are the particulate TiO of granularity 5nm to 200nm ₂

20. the described UV-A shading composition of claim 18, wherein the polymer class UV screening agent is an organo-siloxane.

21. the described UV-A shading composition of claim 20, wherein organo-siloxane is the organo-siloxane that contains the phenylmalonate ester group.

22. in the claim 1 to 15 any one the purposes of the compound that defines in preparation UV-A sun-screening agent.